KR20010069202A - Bituminous emulsions, and their use for the production of materials and of road pavements - Google Patents

Abstract

PURPOSE: Provided are a bituminous emulsions, their use in materials and coatings for roads, in which the addition of a specified surfactant to the bituminous emulsion enables the preparation of road surface coatings which stabilize quickly to allow re-opening to traffic. CONSTITUTION: The bituminous emulsion comprises a binder, water, a cationic, anionic or non-ionic emulsifier and also a surfactant additive selected from: (a) a non-ionic polyoxyethylated surfactant conforming to the crude formula: Rx(O(C2H4))yOH or RxCO(O(C2H4))yOH; (b) a product of the formulae above; (c) an amphoteric surfactant, alone or mixed, of the crude formula: Rx(N¬+(CH3)2)(CH2)yA or RxNH(CH2)yCOOH or RxNH(CH2)yB,C; (d) amphoteric surfactants of formulae as in (c); (e) an alkanolamide surfactant of crude formula: RxCONH(CH2)yOH or RxCONH((CH2)yOH)((CH2)zOH); Rx represents chains as in (a); (f) N amine oxide of crude formula: Rx(CH3)2NO; Rx represents chains as in (a); Rx = a carbyl chain(optionally unsaturated and substituted), an alkyl(ene)phenyl or either of these in which H is partially or totally substituted by F; a poly(dimethylsiloxane) chain (x is the number of Si atoms); x = number of C atoms in the chain; 7 - 22; y = number of ethylene oxide motifs; 0 - 8 (preferably less than or equal to 6) for the first formula; 2 - 8(preferably less than or equal to 6) for the second formula; 0 - 4. A = COO-, OSO3- or OSO2-; B = OSO3- or OSO2-; C = a cationic ion of an alkali, alkaline earth, Fe, Cu, Mn or Zn, or ammonium to impart electrical neutrality; y = number of CH2 motifs; x = 4 - 15; y, z = number of ethylene oxide motifs; z = 1 - 4.

Description

BITUMINOUS EMULSIONS, AND THEIR USE FOR THE PRODUCTION OF MATERIALS AND OF ROAD PAVEMENTS}

The present invention relates to the preparation of bitumen emulsions and to aggregates at roadside temperatures (ie, generally 0 to 40 ° C.) and road pavements obtained from the emulsions.

In most cases, the bitumen emulsion is a bitumen binder, a cationic surfactant-in this case a cationic emulsion-or an anionic surfactant-in this case an emulsion of an anionic emulsion-or a nonionic surfactant-in this case It is called a nonionic emulsion-and contains water. Cationic emulsions are particularly good in terms of the rate of breakage to the aggregate and the adhesion properties generally obtained between the aggregate and the broken emulsion, allowing for the obtaining of road pavements with good mechanical properties obtained. In addition to the above components, cationic emulsions are often acidified by the addition of an acid in the aqueous phase for emulsion preparation, and anionic emulsions are generally prepared in alkaline media.

Bituminous materials obtained by coating or contacting aggregate with bitumen emulsions have long been known. In particular, the distinction between injection, low temperature, open-grade, semi-dense-grade dense-grade and storage-grade mixes, emulsion-stabilized gravels, surface coatings and bonding coats is professionally possible.

For the manufacture of road pavements, the bitumen material of the first form comprises a cold injected mix, in which case it is applied in the form of a "soup" a few seconds after the mix is made, In most cases, the application problem is solved. On the other hand, it goes through an essential step of increasing cohesion, which is generally carried out without external stresses by chemical and physical changes in the system, but in some cases a compacting operation is performed. This change involves the coalescence of the emulsion and is accompanied by the spontaneous start of the aqueous phase. The first phenomena is very well controlled by those skilled in the art who can control the nature and amount of emulsion formation and destruction additives, but there are still no technical solutions to control the second phenomena, sometimes resulting in insufficient adhesion. Can be.

Bitumen materials of the second form include open-grade, semi-dense- and dense-grade cold mixes, storage-grade cold mixes, and emulsion-stabilized gravel, and the optimized selection of emulsions (the nature and amount of emulsions) , Bitumen concentration, pH), in many cases, makes the part of the coating, transport and application of the expanded form of the mix partially or fully resolvable. However, once the expanded mix is electrodeposited in the form of pavement, it is necessary to perform a pressing step to increase adhesion, i.e. good adhesion between bitumen and aggregate, to prevent temporary inhibition during application or road renovation when the pavement is being transported or repaired. To withstand. This adhesion is obtained by mass compaction, accompanied by the withdrawal of the aqueous phase and air. The low temperature coating material exhibits a high degree of friction, which hinders the compaction operation, and the compressibility obtained at low temperatures is very often worse than that obtained using the same material coated at high temperature with the same binder. However, as is known to those skilled in the art, the degree of compaction and the degree of water withdrawal during compression allow for the evaluation of the adhesion of low temperature dense material. Thus, it has been found that the successful construction of roads now under heavy traffic (T1 or higher) depends not only on the technology, but also on the weather conditions on the day when the operation is performed and even on the next day. Bright sunshine, high temperatures or strong winds contribute to the drying and increased adhesion of the packaging material.

In all of these cases of cold mix application (storage-grade, open-grade, semi-dense-grade, dense-grade and injected mix and emulsion-stabilized gravel), the rapid re-opening of traffic, the more traffic It provides a lot of problems. In the case of premature opening, the water film generally present between the coarse aggregate particles and the binder coat prevents adhesion formation between the binder and the aggregate. There is a loss of aggregate, which weakens the packaging material against pounding and at the same time worsens its surface quality. When the road is (re) opened to traffic, only evaporation drying causes the aqueous film to disappear. Therefore, it is advantageous to be able to remove as much water as possible during the application period and also to increase the effect of the packaging material pressing operation.

Bitumen materials of the third type contemplated herein are obtained by continuous application of one or more aggregate courses that soak during compression by setting-in of aggregate particles in the emulsion in one or more bitumen emulsion coating and breaking processes. Surface coatings. In order to prevent the emulsion once applied to the ground, especially on sloped roads, from flowing beyond the boundaries of the road under manufacture, for example, by increasing the amount of bitumen it contains above 65 volumes, or otherwise It is necessary to increase the viscosity by adding modifiers, and increasing the concentration of bitumen binder generally impairs the fineness of the emulsion, which can cause stability problems during storage. Even without operating at high bitumen binder concentrations, the fact that the level of emulsion reactions for coatings is high means that little emulsifier is used, which can be a long term storage problem. Bitumen materials of the third type are also obtained by spraying rapidly breaking emulsions and often comprise a bonding coat which is used at high temperatures on a support. Since the breakdown must be rapid, the amount of emulsifier used is small, which can also cause stability problems during long-term storage. These problems are more serious when the binding emulsion contains a low permeability bitumen binder, which is a situation with a binding coat without surface adhesion, which is difficult to emulsify bitumen.

Indeed, the behavior of prior art low temperature mixes appears to be greatly influenced by the amount of added water, and the useful water-content range is narrow, so that water-content must be tightly controlled in order to obtain a satisfactory quality road pavement. . Thus, in order to avoid any undesirable departure that may harm the quality of the final road pavement, the entire emulsion preparation process, then the mix, and finally very tight control of the road pavement is required. It is therefore also advantageous to be able to reduce the sensitivity to the amount of added water in the behavior.

The present invention surprisingly shows improved water withdrawal spontaneously for the first form, without squeezing for the first and second forms, and immediately after application and during squeezing without squeezing for the first and second forms, A bitumen emulsion, a low temperature mix and an emulsion-stabilized gravel (first and second forms above), which can be used to prepare road paving materials which surprisingly show improved compressibility to the road pavement of the technology, are presented here The bitumen emulsions and mixes are stored and do not alter the operating conditions during their manufacturing steps during possible transportation, unloading, application and possible compression. The present invention also proposes surface-coating emulsions and surface coatings, and bond-coat emulsions and bond coats (type 3), which can be used in the production of road pavements. These emulsions have improved storage capacity and can have higher viscosity without using prior art viscosity modifiers and also without increasing the concentration of bitumen. The present invention provides a glass that allows road pavement material to be obtained that can be re-opened very quickly for road traffic, without having to wait hours or days for evaporation of residual aqueous phases that have not been removed during breakage of the emulsion and possibly compression. This is especially true of road innovation. The rapid stabilization of the road pavement material according to the invention is clearly economically advantageous.

Compared with the emulsions and mixes of the prior art, the behavior and quality of the road pavement materials obtained in these were greatly influenced by the amount of added water, but the emulsions and mixes according to the present invention would yield a road pavement material of good quality. It also allows for significant changes and departures in the amount of added water. This operating margin helps to prepare the mix of the present invention.

The emulsions according to the invention are characterized in that they contain bitumen binders and water, at least one surfactant additive, in addition to the usual cationic, anionic or nonionic emulsifier (s). These surfactant additives are used singly or collectively, from the end of emulsification of the emulsion to its use in the emulsion phase according to the art, or in the emulsion, using cationic, anionic or nonionic emulsifiers prior to preparation of the emulsion. In emulsions prepared according to the art using cationic, anionic or nonionic emulsifiers at any time, it can be mixed with cationic, anionic or nonionic emulsifier (s) prior to the preparation of the emulsified or dispersed phase. Water may be added to wet the aggregates. In this case, water can be added using a nonionic emulsifier to facilitate dispersion, or it can be done in an acid medium in the presence of a cationic emulsifier or in a basic medium in the presence of an anionic emulsifier. It is also possible to incorporate portions of the surfactant additives in the emulsion and the remainder of the added water which serves to wet the aggregates. In this specification, emulsifiers and surfactant additives (surfactants) are distinguished. In other words, an emulsifier is a chemical substance which makes it possible to add a bitumen binder into an emulsion, within the meaning of the prior art, while the surfactant additive is added to the bitumen emulsion preparation according to the prior art to obtain a bitumen emulsion according to the invention. It is a chemical that makes it possible.

The surfactant additives used in the cationic, anionic or nonionic emulsions according to the invention can in particular be selected from the following:

a-polyethoxylated nonionic surfactant, alone or in a mixture of the general formula:

R _x [O (C ₂ H ₄ )] _y OH or R _x CO [O (C ₂ H ₄ )] _y OH

(In the meal,

R _x represents a substituted or unsubstituted, saturated or unsaturated straight or branched carbon chain, or alkyl (ene) phenyl, or one of the chains where hydrogen is partially or completely substituted by fluorine, and x is a carbon chain Or carbon number of alkyl (ene) phenyl, y represents number of ethylene oxide units;

For molecules corresponding to the first approximate chemical formula, 7 ≦ x ≦ 22, 0 ≦ y ≦ 8, preferably y ≦ 6,

For molecules corresponding to the second approximate formula, 7 ≦ x ≦ 22, 2 ≦ y ≦ 8, preferably y ≦ 6).

Preferred nonionic surfactants by the applicant are selected from the following, alone or as a mixture:

Polyethoxylated alkyl (ene) ethers of 6 ≦ x ≦ 22, 2 ≦ y ≦ 6,

Polyethoxylated alkyl (ene) esters of 5 ≦ x ≦ 21, 2 ≦ y ≦ 6,

Polyethoxylated alkyl (ene) phenols of 6 ≦ x ≦ 22, 2 ≦ y ≦ 6;

b-polyethoxylated nonionic surfactant, alone or as a mixture, of the general formula

R _x [O (C ₂ H ₄ )] _y OH or R _x CO [O (C ₂ H ₄ )] _y OH

(In the meal,

R _x represents a straight or branched poly (dimethylsiloxane) chain, x represents the number of silicon atoms, y represents the number of ethylene oxide units,

4 ≦ x ≦ 15 and 4 ≦ y ≦ 20);

c-zwitterionic surfactants alone or as a mixture of the general formula:

R _x [N ⁺ (CH ₃ ) ₂ ] (CH ₂ ) _y A or R _x NH (CH ₂ ) _y COOH or R _x NH (CH ₂ ) _y B, C

(In the meal,

R _x represents the same chain as in a-, A represents a COO ^- group or OSO ₃ ^- group or OSO ₂ ^- group, B represents an OSO ₃ ^- group or OSO ₂ ^- group, and C is a salt that is electrically neutral In a proportion such that an alkali or alkaline earth metal, a cationic counterion of iron, copper, manganese or zinc, or an ammonium cation, y represents the number of CH ₂ units,

7 ≦ x ≦ 22 and 0 ≦ y ≦ 4);

d-zwitterionic surfactants, alone or as a mixture of the general formula:

R _x [N ⁺ (CH ₃ ) ₂ ] (CH ₂ ) _y A or R _x NH (CH ₂ ) _y COOH or R _x NH (CH ₂ ) _y B, C

(In the meal,

R _x represents the same chain as in b-, A and B represent the same group as in c-, C represents the same ion as in c-in a ratio such that the salt is electrically neutral, y Represents the number of CH ₂ units,

4 ≦ x ≦ 15 and 0 ≦ y ≦ 4);

e-alkanolamide surfactant, alone or as a mixture, of the general formula

R _x CONH (CH ₂ ) _y OH or R _x CON [(CH ₂ ) _y OH] [(CH ₂ ) _z OH]

(In the meal,

R _x represents the same chain as in a − above,

7 ≦ x ≦ 22 and 1 ≦ y ≦ 4 and 1 ≦ z ≦ 4);

f-amine-oxide surfactants, alone or as a mixture of the general formula:

R _x (CH ₃ ) ₂ NO

(In the meal,

R _x represents the same chain as in a − above,

7 ≤ x ≤ 22).

The concentration of nonionic surfactant additive (s) in the emulsions according to the invention is generally at least 0.2 kg and not more than 8 kg per tonne of emulsion. The degree of addition of the surfactant additive is assessed for the concentration of cationic, anionic or nonionic emulsifier (s) used by those skilled in the art. The concentration of surfactant additive (s) used therefore depends on the type of bitumen material to be prepared. In general, this concentration does not exceed the concentration of the cationic, anionic or nonionic emulsifier (s) of the emulsion. The chemical nature and amount of surfactant additive (s) to optimize the application properties depends on the aggregate used in the first and second form bitumen materials.

Among the cationic emulsifiers that can be used to prepare the cationic emulsions and bitumen materials according to the invention, cationic emulsifiers which are commonly used, in particular the following:

* Alkyl (alkylene) polyamine, and more particularly tallow (poly) propylene polyamines, for example tallow propylene diamine (EINECS defined as marketed DINORAM ^ⓡ from Ceca SA: amine, N- tallow-alkyl-trimethylene di -, RN = 61791- 55-7), tallow dipropylenetriamine (amine, (N-tallow) alkyldipropylenetri-, RN = 61791-57-9) and tallow tripropylenetetramine (amine, (N-tallow) tripropylene tetra-alkyl -, RN = 68911-79-5) (the latter also known well POLYRAM ^ⓡ available from Ceca SA, Inc.),

* Alkoxylated alkyl (ene) polyamines, more particularly propoxylated tallow dipropylenetriamine (amine, (N-tallow), 2-propanol-[[[(3-aminopropyl) amino] -3-propyl] "bis-imino] -1,1, RN = 97592-79-5) (the latter also known as well POLYRAM ^ⓡ, available from Ceca SA, Inc.).

Methyl chloride is well known as STABIRAM ^ⓡ MS3 available from - (, chloride, RN = 68607-29-4 consisting of a quaternary ammonium ion, tallow-alkyl-trimethylene di-pentamethyl), Ceca SA Company * quaternary ammonium salt, e.g. Quaternized tallow propylenediamine;

Alkyl (ren) amidoamines, more specifically tallow or deoiled alkyl (ren) amidoamines, alkylimidazoline cyclized derivatives thereof, or mixtures thereof (C ₈ -C ₂₂ fatty acids and C _2- Produced by condensation with C ₃ polyalkylene polyamines and ethanolamines, mixtures thereof and the resulting amide cyclized products), which is well known as emulsifier L60 from Ceca SA.

The concentration of cationic emulsifier (s) of the emulsion according to the invention is generally at least 0.8 kg and at most 30 kg per ton of emulsion. The concentration of cationic emulsifier (s) used also depends on the type of bitumen material to be prepared.

Usually, it is desirable to add an amount of acid to the aqueous phase of the cationic emulsifier (s).

Anionic emulsifiers that can be used in the preparation of the anionic emulsions and bitumen materials according to the invention are conventional anionic emulsifiers, in particular alkyl (lene) carboxylates, alkyl (lene) sulphates and alkyl (lene) sulfonates, alkyl ( Lene) aryl (lene) carboxylate, alkyl (lene) aryl (lene) sulfate and alkyl (lene) aryl (lene) sulfonate, and also alkyl (lene) (aryl (ene)) phosphoric esters. Wherein the alkyl (alkenyl) or alkyl (lene) (aryl (ene)) chain has 8 to 22 carbon atoms. It is usually desirable to add an amount of base to the aqueous phase of the anionic emulsifier (s).

The concentration of the anionic emulsifier (s) of the emulsion according to the invention is generally at least 0.8 kg and at most 30 kg on the emulsion tone. The concentration of anionic emulsifier (s) used also depends on the type of bitumen material to be prepared.

Nonionic emulsifiers that can be used in the preparation of the nonionic emulsions and bitumen materials according to the invention are conventional nonionic emulsifiers, in particular alkyl (ene) poly (oxyethylene) alcohols and alkyl (ene) aryl (ene) poly (oxyethylene) Selected from alcohols, wherein the alkyl (alkenyl) chain has from 8 to 22 carbon atoms and the number of ethylene oxide units is at least 9;

The concentration of nonionic emulsifier (s) of the emulsions according to the invention is generally at least 0.8 kg and at most 20 kg on the emulsion tone. The concentration of nonionic emulsifier (s) used also depends on the type of bitumen material to be prepared.

The bitumen binder used may be selected from the bitumen materials commonly used in bitumen emulsions of the first, second and third form materials, and their permeability is generally 20/30 to 500.

Emulsions can be prepared with one or more binders, and when using multiple binders, the various binders are mixed at high temperature prior to emulsification, or two (or more) emulsions are prepared, each of which is used to prepare a mix. And a binder that is mixed continuously to produce a so-called hybrid emulsion that is brought into contact with the aggregate. An example of the preparation of a hybrid bitumen emulsion is described in detail in the patent EP 589,740 B1 in the name of the applicant, the content of which is hereby incorporated by reference, in which the patent, while maintaining good mechanical strength of the final road pavement material, As hybrid emulsions for improving the workability of the mix, one describes a hybrid emulsion based on a soft bitumen binder and the other based on a hard bitumen binder.

Subject of the invention is also a road pavement material obtained from the first and second form bitumen materials, and the following:

A bitumen emulsion according to the invention as defined above, aggregates wetted with additive water, possibly containing one or more surfactant additives;

Aggregate wet with additive water, containing conventional bitumen emulsions (ie, containing no surfactant additives as defined above) and one or more surfactant additives.

Cold forms of these forms (first and second forms), ie infused mix, open-grade, semi-dense- and dense-grade mix, storage-grade mix and emulsion-stabilized gravel, are known Obtained by mixing the bitumen emulsion and the wet aggregate with the additive water in accordance with known techniques using the equipment. In this case, what is to be obtained is an improved degree of compaction and a significant amount of water once all steps have been carried out before opening to traffic. According to the invention, in the case of emulsion-stabilized gravels, storage-grade or cold open-grade mixes, cold semi-dense grade mixes and cold dense-grade mixes, enhanced water leaching occurs during compression. The improvement in the degree of compaction is visible at the end of the compression. According to the invention, for cold injected mixes, improved water rejection takes place in a spontaneous manner without external stress. In the latter case, the degree of compaction may be improved even if there is actually no external stress by self-compression under the influence of gravity. In order to improve the intermediate and final adhesion, a compacting step can be carried out, in which case the reduction in porosity and the increase in water withdrawal are greater for the first form mix according to the invention. In the case of materials of this form (first form and second form), no modifications are necessary to the equipment or setting, by carrying out the coating, emulsion-breaking, possible transport, unloading and application steps in the same manner.

Low temperature (type 3) surface coatings are prepared by applying one or more bitumen emulsion coats and one or more aggregate courses as a way to successfully cover the surface to which the road pavement is to be placed using standard techniques and equipment. The road pavement here is obtained after the breakdown and compression of the emulsion. In the case of steep slope supports, high emulsion viscosity is required. Currently used solutions consist of increasing the bitumen concentration by more than 65 and / or adding thickeners to the continuous phase. In addition, when the reactivity required for the emulsion is high, and a small amount of emulsifier is used, the problem of storage stability of the coating emulsion is often caused. The problem which arises at the time of manufacture and use of the emulsion for bond coats (type 3) is the same. It is more difficult to emulsify, which is even worse when one wants to use a binder with a low passability, which is the case for an "tack-free" bond coat. In accordance with the present invention, sufficient addition of the surfactant additives described above to formulations used by those skilled in the art will result in an increase in viscosity without modifying the emulsion (if added to the oil phase), Fracture kinetics hardly change. In addition to the addition of higher amounts of surfactant additives, it may be necessary to adjust to raise the amount of nonionic, anionic or cationic emulsifiers used by those skilled in the art to keep the fracture kinetics constant. . In this case, emulsification and storage stability are greatly improved, and the viscosity increases. In other words, by adding the surfactant additive according to the present invention, it is possible to obtain modified fracture kinetics-a viscosity high enough to avoid the fracture problem-and also improved storage stability.

Example

Preparation of Emulsion

In Examples 1-4, cationic bitumen emulsions are prepared from a mixture of cationic emulsifiers, acids, bitumen binders and water, and surfactant additives are added thereto just prior to the start of the phase mixing with the aggregate to produce a mix.

In Examples 5, 7 and 8, cationic surfactant bitumen emulsions are prepared from water (with nonionic surfactant additives added), cationic emulsifiers, acids and bitumen binders.

In Example 6, a cationic bitumen emulsion containing no nonionic surfactant additive is prepared and prepared from the emulsion by mixing the mix according to the present invention with aggregates wetted with additive water, which contains a nonionic surfactant additive. , Cationic surfactants and acids are added.

In Example 9, a cationic bitumen emulsion was prepared from a mixture of a cationic emulsifier, an acid, a bitumen binder and water, and thereon a nonionic surfactant based on a fluoroalkyl chain just prior to the start of the phase where it was mixed with aggregate to produce a mix. Additives are added.

Manufacture of mix

The aggregates are placed in a planetary mixer (SR Consulting, type SRC5A, rotational speed: 30 rpm) and mixed for 30 seconds. Then, the added water is injected and the mixing is continued for another 30 minutes before adding the emulsion. After the mixing of all the components in the mix is continued for 1 minute, the resulting mixture is introduced into the mold and stored in the kettle for 1 hour before pressing.

Manufacture of road pavement

Compress the mix using a Gyratory Shear Compactor (Invelop Oy ICT-100RB model). The mix is removed from the reaction bath, placed in a GSC mold (cylindrical mold, diameter: 100 mm, height: 25 cm), and then subjected to a pressure load of 1 MP clearance angle, 0.6 MPa for N rotation. The number of revolutions performed depends on the type of application. That is, 30 revolutions for the cold open-grade mix and 120 revolutions for the cold dense-grade mix. At the end of the compression, the test piece is weighed again to calculate the of the water removed during the compression. Pore content is calculated by measuring the packaging material height before and after compression.

Performance evaluation

The degree of improvement of the performance of the emulsion and the road product according to the present invention is evaluated by comparing the preparation according to the prior art (with no surfactant additive) and the preparation according to the present invention (containing the surfactant additive). In order to validate the comparison in the following test, the same cationic emulsifier is used in both formulations. On the other hand, in some cases, the concentration of the cationic emulsifier is different for both formulations, maintaining similar fracture kinetics, thereby keeping the settings used in the filter constant. The expression "similar fracture kinetics" is understood as the average kinetics that the time taken for the emulsion to break does not change by more than 25 (visual assessment). Indeed, in the presence of surfactant additives, at constant concentrations of cationic emulsifiers, the breaking kinetics are required to change, thereby modifying the settings used in the field, some of which may be undesirable.

Example 1 Low Temperature Open-Grade Mix

Cold open-grade mixes are prepared according to the above method of operation. The aggregate used is hornfels and its particle size distribution is as follows:

0/2 mm 44

2/4 mm 12

6/10 mm 44

The filler content (aggregate particles passing through the 80 μm screen) is about 8 weights.

The amount of added water in the mix is 4 g per 100 g of aggregate.

The bitumen emulsion contains the following:

* 61 volumes, 70 transmittance bitumen (commercially available),

* Per 1000 kg of water + bitumen, 6 kg of cationic emulsifier (Ceca commercially available POLYRAM® SL, acidified with hydrochloric acid, the pH of the soap is 2),

* Additive water + bitumen + cationic surfactant additive + alcohol per 1000 kg of acid, 1.3 kg of nonionic surfactant (fatty chain (oleic acid) with 18 carbon atoms, sold under the trade name ROFANOL, per mole of average alcohol, ethylene jade Ethoxylated to 4.5 moles of seed). The bitumen content in the mix is 6 g per 100 g of aggregate.

Under the same operating conditions, for comparison, low temperature mixes are prepared using bitumen emulsions, aggregates and added water which differ from the bitumen emulsions in that they contain no nonionic surfactants.

According to the above method of operation, for each cold mix, three compression tests are performed. In each test, after 30 revolutions, the water withdrawal and porosity at the end of the crimping operation are determined and the mean value is calculated for these three tests. The results are shown in Table 1.

Mix form Exam number Porosity () Ejected Water () Open-grade mix free of nonionic surfactants 1-1 17.3 15 1-2 17.7 17 1-3 17.4 18.4 Average 17.5 16.8 Open-grade mix according to the invention 1-4 16.7 25.4 1-5 16.3 23.7 1-6 16.5 23.3 Average 16.5 24.1

The presence of nonionic surfactants has been found to increase the water leaching and final compaction of the mix.

It is also pointed out that, on average, the appearance of water occurs more quickly in the case of mixes containing nonionic surfactants, but the breakdown kinetics of the two emulsions are similar.

Example 2 (cold open-grade mix)

According to this method of operation, a low temperature open-grade mix is prepared. The aggregates, bitumen and cationic emulsifiers used are the same as those of Example 1, and the contents of the aggregates, added water, bitumen and cationic surfactants used are the same as for the mix of Example 1. On the other hand, the nonionic surfactant used is an acid based on an aliphatic chain (oleic acid) having 18 carbon atoms, which acid is ethoxylated with 6 moles of ethylene oxide per mole of an average acid, which is water + bitumen + cationic surfactant + To 1000 kg of acid is added to the already prepared emulsion in an amount of 1.6 kg.

Under the same operating conditions, for comparison, low temperature mixes are prepared from bitumen emulsions different from those defined above in that they contain no nonionic surfactants.

Three compression tests are performed for each cold mix according to the method of operation. In each test, after 30 revolutions, water withdrawal and porosity at the end of the crimping operation are measured and the mean value is calculated for these three tests. The results are shown in Table 2.

Mix form Exam number Porosity () Ejected Water () Open-grade mix free of nonionic surfactants 2-1 16.55 18 2-2 17.8 17 2-3 18.6 16.3 Average 17.65 17.1 Open-grade mix according to the invention 2-4 16.3 27.55 2-5 17.1 19 2-6 16.8 20 Average 16.7 22.2

The mix according to the invention of example 2 has a higher degree of rejection of the aqueous phase and a higher final crimp value than the mix without a nonionic surfactant, but less than the mix according to the invention of example 1.

Note that in the case of a mix containing a nonionic surfactant, water leaching occurs more rapidly than in the case of a mix containing no nonionic surfactant, but the breakdown kinetics of the two emulsions are similar.

Example 3 (cold open-grade mix)

According to the above method of operation, a low temperature open-grade mix is prepared from the same aggregate used to prepare the mix of Examples 1 and 2 and used in the same proportions as in the above examples, and the content of the added water of the mix is Same as the case of the mix of 1 and 2.

According to the method described in patent EP 589,740 B1, 60 parts by weight of the first emulsion containing 61 volume of bitumen having a residual binder permeability of 70, 61 volumes of bitumen and 300/61 volumes of 61 volume A hybrid emulsion obtained by mixing 40 parts by weight of a second emulsion containing 400 permeable bitumen is prepared [wherein the first bitumen is available from Elf, and the first and second emulsions are each 1000 kg of water + bitumen. , it contains a POLYRAM ^ⓡ SL of 6 kg (acidified with hydrochloric acid, the pH of the soap being 2).

If the Hebrew de Emulsion The above two prepared from emulsions, where after the alcohol NACOL ^ⓡ of nonionic surfactants, sugar alcohol mole with ethylene oxide of 4 moles, fat chains substrate having a carbon number of 10 (, NACOL ^ⓡ 4 Per 1000 kg of water + bitumen + cationic surfactant + acid, a nonionic surfactant is added in an amount of 1.8 kg. Under the operating conditions described above, a mix of these hybrid emulsion substrates is prepared and then pressed. The bitumen content is 6 g per 100 g of aggregate.

For comparison, under the same operating conditions, a mix obtained from an emulsion without the addition of a nonionic surfactant is prepared and pressed.

The compression results are shown in Table 3, and the porosity and water exit are calculated at the end of the compression after 30 revolutions.

Mix form Exam number Porosity () Ejected Water () Open-grade mix free of nonionic surfactants 3-1 17.7 15.2 3-2 18.05 12.7 3-3 18 14 Average 17.9 14 Open-grade mix according to the invention 3-4 17.1 18.3 3-5 17.4 18.4 3-6 17.2 17.7 Average 17.2 18.1

Leaching and compaction of the aqueous phase improved in the presence of nonionic surfactants, while water retreat occurred on average four times, whereas for non-ionic surfactant mixes, retirement occurred only on average after 26 revolutions. It is pointed out that the destruction kinetics of the two emulsions are similar.

Example 4 (cold semi-dense-grade to dense-grade mix)

Low temperature half-dense to dense-grade mixes are prepared according to the operating method described in Example 3.

The granular aggregates used, by nature, have the following particle size distribution:

0/2 mm 39

6/10 mm 61

Its filler content is about 7.5. The amount of added water is 6 g per 100 g of aggregate.

A hybrid emulsion having a residual binder permeability of 80 was prepared, which emulsion contained 63 volumes of bitumen, 60 parts by weight of the first emulsion containing 63 volumes of 20/30 permeability bitumen, and 63 volumes of 500 permeability. is obtained by mixing a second emulsion 40 parts by weight containing bitumen [here, the first bitumen and Elf is commercially available, the first and second emulsions each containing POLYRAM ^ⓡ SL of water +, 6 kg per bitumen 1000 kg (\ (Acidified with hydrochloric acid so the pH of the soap is 2)) The bitumen content is 5.7 g per 100 g of aggregate.

For comparison, a mix based on the hybrid emulsion, aggregate and added water is prepared and pressed.

Using this hybrid emulsion, 3 hybrid emulsions are prepared by adding the following:

- in the case of the first emulsion, water + + bitumen cationic surfactant acid + 1000, 1.85 kg per kg an amount of NACOL ^ⓡ 4 OE (Emulsion in accordance with the present invention),

Alcohol NACOL having 12 moles of ethylene oxide per mole of alcohol as the alcohol based on a fatty chain of 10 carbon atoms in an amount of 1.85 kg per 1000 kg of water + bitumen + cationic surfactant + acid for the second emulsion. ) (Hereafter referred to as NACOL 12 OE),

For the third emulsion, water + bitumen + cationic surfactant + alcohol ROFANOL ^® (emulsion according to the invention), based on the essential oleic fat chain, in an amount of 2 kg, per 1000 kg of acid.

Subsequently, three mixes based on the three emulsions, the aggregate and the added water are prepared and pressed in the above ratio. The results are shown in Table 4. Porosity and water withdrawal are calculated at the end of the compression after 120 revolutions.

Mix form Exam number Porosity () Ejected Water () Semi-dense-grade mix containing no nonionic surfactant 4-1 11.15 53.7 4-2 10.7 54.6 4-3 11.6 50.4 Average 11.2 52.9 Semi-dense-grade mix containing NACOL 4 OE according to the invention 4-4 9.8 62.5 4-5 9.63 63.5 4-6 10.4 61.75 Average 9.9 62.6 Semi-dense-grade mix with NACOL 4 OE 4-7 10.9 49.6 4-8 11.4 53.1 4-9 11.1 52.6 Average 11.1 51.8 Dense-grade mix according to the invention containing ROFANOL ^® 70/75 4-10 9.1 65.3 4-11 9.2 67.6 4-12 8.9 66.8 Average 9.1 66.6

NACOL ^ⓡ 4 OE non-ionic surface active agent, by squeezing the emulsion and ROFANOL ^ⓡ a 70/75 mix of the present invention prepared from an emulsion containing a surfactant containing a compression degree and water exit is obtained, NACOL ^ⓡ 12 OE non Larger than those obtained by compressing a mix made from an emulsion containing an ionic surfactant or a mix made from a hybrid emulsion containing no nonionic surfactants.

Also, NACOL destruction rate of emulsion containing 12 OE ^ⓡ is noted that is slower than the case containing no case of emulsions containing NACOL ^ⓡ 4 OE (at the same rate) and a non-ionic surfactant at all. Destructive dynamics of emulsifiers containing ROFANOL ^ⓡ 70/75 is slightly different from that of the reference emulsion.

Based on the hybrid emulsion distinguished from the emulsion containing NACOL ^® 12 OE in that it contains 0.5 kg of NACOL ^® 12 OE instead of 1.85 kg for 1000 kg of water + bitumen + cationic emulsifier + acid When another mix is prepared and pressed, the emulsion breaks faster than an emulsion containing almost three times the amount of nonionic surfactant, but more slowly than an emulsion containing no nonionic surfactant. . In addition, water + bitumen + cationic emulsifier + acid Hebrew de case be produced by compressing the mix to the emulsion as a base material, squeezed, road and water exit the non-ionic surfactant containing NACOL ^ⓡ 12 OE in the art, 0.5 kg 1000 kg It was found to stay at the level of the control group.

Example 5 (cold open-grade mix)

The aggregate used is the same as in Example 1.

The content of aggregate, bitumen and added water is the same as in Example 1.

The emulsion contains the following:

* 60 volumes of bitumen described in Example 1,

* Water + SL of bitumen POLYRAM ^ⓡ, 6 kg per 1000 kg (acidified with hydrochloric acid, the pH of the soap being 2),

* Water + bitumen + cationic emulsifier + 3 kg of ROFANOL ^® per 1000 kg of acid.

A mix according to the present invention based on the emulsion, aggregate and added water, and a mix based on an emulsion containing no nonionic surfactant for comparison, are prepared and pressed.

The results are shown in Table 5.

Mix form Exam number Porosity () Ejected Water () Open-grade mix free of nonionic surfactants 5-1 17.5 22.8 5-2 16.9 23.2 5-3 17.1 23 Average 17.2 23 Open-grade mix according to the invention 5-4 16 30.7 5-5 15.8 30.9 5-6 16.1 30.5 Average 16 30.7

It has been found that the degree of compaction and exit of the aqueous phase of the compacted mix according to the present invention is improved over the compacted mix which contains no nonionic surfactants.

Withdrawal of the fluid in the case of the compacted mix according to the invention takes place faster than for the compacted mix which contains no nonionic surfactants (average, after 5 revolutions instead of 22 revolutions). The fracture kinetics of the two emulsions are similar.

Example 6 (cold open-grade mix)

Here, examples of the 5, the compression of the mixes prepared in an emulsion which does not contain a nonionic surfactant, water per 100 parts by weight, POLYRAM ^ⓡ SL (cationic emulsifier) 0.37 parts by weight, ROFANOL ^ⓡ 0.37 parts by weight , addition-be-the pH of the solution based on the amount of hydrochloric acid such that 5, the same aggregates and advance from the number of the addition, 6 non-ionic in kg instead of example 5 in that it contains a POLYRAM ^ⓡ SL of 5 kg surfactant Compared to the compression of the mix made from the same proportion of emulsion, which is distinct from the emulsion without. Aggregate, bitumen and addition-water-solution contents are the same as in Example 1.

The results are shown in Table 6.

Mix form Exam number Porosity () Ejected Water () Mixes that do not contain nonionic surfactants One 17 22 Mix according to the present invention One 15.9 25.6

Porosity and water rejection are calculated at the end of the compression after 30 rotations, and it has been found that the water rejection and compaction of the mix according to the present invention is better than for a mix containing no nonionic surfactant.

In the case of a compacted mix according to the invention, the fluid is withdrawn more quickly than in the case of a compacted mixture containing no nonionic surfactant: after 15 revolutions, instead of an average of 22 revolutions. Fracture kinetics are similar.

Example 7 (cold injected mix)

Cold injected mixes are prepared according to the above method of operation.

The aggregate used is microdiorite, and its particle size distribution is as follows:

0/2 mm 55

2/6 mm 45

It falls within the Form III ISSA grade range and has a filler content of 10 weights.

The added water content is 10 g of water per 100 g of aggregate.

The bitumen emulsion according to the invention contains the following:

* 61 of 70/1000 penetrating Via Total bitumen,

* Water + bitumen 1000 kg sugar, POLYRAM ^ⓡ S of 10 kg (acidified with hydrochloric acid, the pH of the soap 2 Im) (which is water + bitumen + cationic emulsifier + acid 1000 kg sugar, 2.5 kg of ROFANOL (trade name) and Mixed). The bitumen content is 7 g per 100 g of aggregate.

For comparison, an emulsion is prepared which is distinguished from the former in that it contains no nonionic surfactant at all.

The aggregate wetted with additive water is mixed with one or more of the emulsions using a spatula in a reaction bath until the emulsion breaks.

In the case of the mixes prepared from the emulsions according to the invention, it was found that destruction occurred faster than those prepared from the emulsions according to the prior art (invention: 1 minute 40 seconds, prior art: 2 minutes 10 seconds).

Both mixes based on the same proportions of identical components are prepared in the reaction bath, the manual mixing is stopped just before the emulsion is destroyed, and the reaction bath is tilted to determine the time it takes for the first drop of water to break down the mix heap.

In the case of the mix according to the invention, the first drop of breaking water appears after 2 minutes, whereas in the case of the mix according to the technique, after 4 minutes.

In the case of the tested amount mix, the amount of water to break is comparable.

Example 8 (Surface Coating)

A bitumen emulsion is prepared containing the following:

* 69 volumes of 180/220 transmission Elf bitumen (available from Elf),

* Cationic emulsifier marketed under the trade name DINORAM ^® S for 3 kg per 1000 kg of water + bitumen.

The breakdown index of this emulsion is 100 and the viscosity is 6 ° E, which in this case is considered to be too low. The D-S difference corresponding to the water concentration difference of the emulsion between the upper and lower ends of the storage container and representing the storage sensitivity according to the ASTM D 244-89 test represents water 4 on day 7.

For the same ingredients, more viscous, containing the same proportions of bitumen, containing 4.5 kg of DINORAM® S and 2 kg of ROFANOL® per 1000 kg of water + bitumen + cationic emulsifier Prepare an emulsion. The fracture index of this emulsion is 90, the viscosity is 12 ° E, and the D-S difference is water 1 on the seventh day.

Example 9 (cold open-grade mix)

The aggregate used is as in Example 1.

Aggregate, bitumen and added water contents are as in Example 1.

The emulsion contains the following:

* 60 volumes of bitumen, described in Example 1,

* Water + SL of bitumen POLYRAM ^ⓡ, 6 kg per 1000 kg (acidified with hydrochloric acid, the pH of the soap being 2),

* Water + bitumen + cationic surfactant + 0.3 kg of FORAFAC 1110D (trade name), commercially available from Atofina, having 10 ethylene oxide units and having a carbon number of 8 perfluoroalkyl chains per 1000 kg of acid ).

A mix according to the present invention, using the above-mentioned emulsion, aggregate and added water, and a mix containing no nonionic surfactant for comparison, are prepared and pressed.

The results are shown in Table 7.

Mix form Exam number Porosity () Ejected Water () Open-grade mix free of nonionic surfactants 1-1 17.3 15 1-2 17.7 17 1-3 17.4 18.4 Average 17.5 16.8 Open-grade mix according to the invention 9-4 16.5 22.2 9-5 16.3 21 9-6 16.7 24.3 Average 16.5 22.5

According to the present invention, the road material (cold injected mix, open-grade, semi-dense-grade and dense-grade mix, cold storage-grade) is easy to handle and is obtained by coating or contacting cold aggregate with bitumen emulsion. Mixtures, emulsion-stabilized gravel, surface coatings and bond coats) can be obtained which can be used.

Claims (12)

A bitumen emulsion containing at least one bitumen binder, water and at least one cationic, anionic or nonionic emulsifier, wherein the bitumen emulsion further comprises at least one of the following surfactant additives: a-polyethoxylated nonionic surfactant, alone or in a mixture of the general formula: R _x [O (C ₂ H ₄ )] _y OH or R _x CO [O (C ₂ H ₄ )] _y OH (In the meal, R _x represents a substituted or unsubstituted, saturated or unsaturated straight or branched carbon chain, or alkyl (ene) phenyl, or one of the chains where hydrogen is partially or completely substituted by fluorine, and x is a carbon chain Or carbon number of alkyl (ene) phenyl, y represents number of ethylene oxide units; For molecules corresponding to the first approximate chemical formula, 7 ≦ x ≦ 22, 0 ≦ y ≦ 8, preferably y ≦ 6, For molecules corresponding to the second approximate chemical formula, 7 ≦ x ≦ 22, 2 ≦ y ≦ 8, preferably y ≦ 6); b-polyethoxylated nonionic surfactants of the general formula: R _x [O (C ₂ H ₄ )] _y OH or R _x CO [O (C ₂ H ₄ )] _y OH (In the meal, R _x represents a straight or branched poly (dimethylsiloxane) chain, x represents the number of silicon atoms, y represents the number of ethylene oxide units, 4 ≦ x ≦ 15 and 4 ≦ y ≦ 20); c-zwitterionic surfactants alone or as a mixture of the general formula: R _x [N ⁺ (CH ₃ ) ₂ ] (CH ₂ ) _y A or R _x NH (CH ₂ ) _y COOH or R _x NH (CH ₂ ) _y B, C (In the meal, R _x represents the same chain as in a-, A represents a COO ^- group or OSO ₃ ^- group or OSO ₂ ^- group, B represents an OSO ₃ ^- group or OSO ₂ ^- group, and C is a salt that is electrically neutral In a proportion such that an alkali or alkaline earth metal, a cationic counterion of iron, copper, manganese or zinc, or an ammonium cation, y represents the number of CH ₂ units, 7 ≦ x ≦ 22 and 0 ≦ y ≦ 4); d-zwitterionic surfactants, alone or as a mixture of the general formula: R _x [N ⁺ (CH ₃ ) ₂ ] (CH ₂ ) _y A or R _x NH (CH ₂ ) _y COOH or R _x NH (CH ₂ ) _y B, C (In the meal, R _x represents the same chain as in b-, A and B represent the same group as in c-, C represents the same ion as in c-in a ratio such that the salt is electrically neutral, y Represents the number of CH ₂ units, 4 ≦ x ≦ 15 and 0 ≦ y ≦ 4); e-alkanolamide surfactant, alone or as a mixture, of the general formula R _x CONH (CH ₂ ) _y OH or R _x CON [(CH ₂ ) _y OH] [(CH ₂ ) _z OH] (In the meal, R _x represents the same chain as in a −, y and z represent the number of ethylene oxy units, 7 ≦ x ≦ 22 and 1 ≦ y ≦ 4 and 1 ≦ z ≦ 4); f-amine-oxide surfactant of the general formula: R _x (CH ₃ ) ₂ NO (In the meal, R _x represents the same chain as in a − above, 7 ≤ x ≤ 22). The bitumen emulsion according to claim 1, wherein the concentration of the surfactant additive (s) is 0.2 to 8 kg, per tonne of emulsion. 3. The alkyl (ene) polyamine, alkoxylated alkyl (ene) polyamine, quaternary alkylammonium salt, alkyl (ene) amidoamine and alkylimidazoline cyclized derivatives thereof according to claim 1, wherein Wherein the alkyl (kenyl) chain has from 8 to 22 carbon atoms) and at least one acid, and preferably at least one acid. The method according to claim 1 or 2, wherein the alkyl (ene) carboxylate, alkyl (ene) sulfate and alkyl (ene) sulfonate, alkyl (ene) aryl (ene) carboxylate, alkyl (ene) aryl ( Ethylene) sulphate and alkyl (lene) aryl (lene) sulfonates, and also alkyl (lene) (aryl (ene)) phosphate esters (where alkyl (alkenyl) or alkyl (lene) (aryl (ene)) chains Anionic bitumen emulsion comprising at least one anionic emulsifier selected from C8-22) and preferably at least one base. 3. The alkyl (ene) poly (oxyethylene) alcohol and the alkyl (ene) aryl (ene) poly (oxyethylene) alcohols wherein the alkyl (alkenyl) chains have from 8 to 22 carbon atoms. And at least one nonionic emulsifier selected from the group consisting of at least 9 ethylene oxide units). The surfactant additive (s) may be cationic emulsifier (s), anionic emulsifier (s) or before emulsification on the emulsification phase before the preparation of the emulsion, or at any time during the end-to-use of the emulsion, or in the emulsion phase before use. A process for producing a bitumen emulsion according to any one of claims 1 to 4, characterized in that it is mixed with a nonionic emulsifier (s). Materials obtained by coating or contacting the following: a) bitumen emulsion as defined in any one of claims 1 to 5, aggregates or road supports, And / or b) aggregates wetted with an aqueous solution containing water or at least one of the following surfactant additives, preferably also containing cationic or anionic surfactants: α-polyethoxylated nonionic surfactants of the general formula: R _x [O (C ₂ H ₄ )] _y OH or R _x CO [O (C ₂ H ₄ )] _y OH (In the meal, R _x represents a substituted or unsubstituted, saturated or unsaturated straight or branched carbon chain, or alkyl (ene) phenyl, or one of the chains where hydrogen is partially or completely substituted by fluorine, wherein x is carbon The number of carbon atoms of the chain or alkyl (ene) phenyl, and y represents the number of ethylene oxide units; For molecules corresponding to the first approximate chemical formula, 7 ≦ x ≦ 22, 0 ≦ y ≦ 8, preferably y ≦ 6, For molecules corresponding to the second approximate chemical formula, 7 ≦ x ≦ 22, 2 ≦ y ≦ 8, preferably y ≦ 6); β-polyethoxylated nonionic surfactants of the general formula: R _x [O (C ₂ H ₄ )] _y OH or R _x CO [O (C ₂ H ₄ )] _y OH (In the meal, R _x represents a straight or branched poly (dimethylsiloxane) chain, where x represents the number of silicon atoms, y represents the number of ethylene oxide, 4 ≦ x ≦ 15 and 4 ≦ y ≦ 20); χ- zwitterionic surfactants, alone or as a mixture, of the general formula: R _x [N ⁺ (CH ₃ ) ₂ ] (CH ₂ ) _y A or R _x NH (CH ₂ ) _y COOH or R _x NH (CH ₂ ) _y B, C (In the meal, R _x represents the same chains as in the α-, A is a COO ^- group or the OSO ₃ ^- group or the OSO ₂ ^- group represents, B is OSO ₃ ^- group or the OSO ₂ ^- group represents, C is the salt is electrically neutral In a proportion such that an alkali or alkaline earth metal, a cationic counterion of iron, copper, manganese or zinc, or an ammonium cation, y represents the number of CH ₂ units, 7 ≦ x ≦ 22 and 0 ≦ y ≦ 4); δ-zwitterionic surfactants, alone or as a mixture of the general formula: R _x [N ⁺ (CH ₃ ) ₂ ] (CH ₂ ) _y A or R _x NH (CH ₂ ) _y COOH or R _x NH (CH ₂ ) _y B, C (In the meal, R _x represents the same chain as in the β-, A and B represent the same group as in the χ-, C represents the same ion as in the χ- in a ratio that causes the salt to be electrically neutral, y Represents the number of CH ₂ units, 4 ≦ x ≦ 15 and 0 ≦ y ≦ 4); ε-alkanolamide surfactant, alone or as a mixture, of the general formula R _x CONH (CH ₂ ) _y OH or R _x CON [(CH ₂ ) _y OH] [(CH ₂ ) _z OH] (In the meal, R _x represents the same chain as in α-, y and z represent the number of ethylene oxy units, 7 ≦ x ≦ 22 and 1 ≦ y ≦ 4 and 1 ≦ z ≦ 4); φ-amine surfactants of the general formula: R _x (CH ₃ ) ₂ NO (In the meal, R _x represents the same chain as in α-, 7 ≦ x ≦ 22); And A bitumen emulsion as defined in any of claims 1 to 5. 8. The material of claim 7 in the form of a low temperature casting mix and the road pavement material obtained. 8. The material of claim 7, wherein the material is in the form of an open-grade mix, a semi-dense-grade mix, a dense-grade mix, a storage-grade mix and an emulsion-stabilized gravel form. Road paving material obtained by pressing the material according to claim 8. The material of claim 7, obtained by continuously applying at least one bitumen emulsion coat, and at least one aggregate course on a road support. 8. The material of the bond coat and bond coat according to claim 7, which is obtained by spraying a bitumen emulsion on a road support.